JPH0312083B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to a method for producing an olefin polymer. More specifically, various polymerization processes (slurry polymerization, bulk polymerization, gas phase polymerization, high temperature solution polymerization,
The present invention relates to a method for producing an olefin polymer using a solid catalyst component that has extremely high activity not only per transition metal but also per solid catalyst in high-pressure ionic polymerization, etc. <Prior art> The high polymerization activity of the catalyst used in the production of olefin polymers means that there is no need to remove catalyst residue from the polymer obtained after polymerization, which can simplify the polymer production process. Needless to say, it has extremely high utility value, but in this case, the catalyst needs to have a high polymerization activity per transition metal as well as a high polymerization activity per solid catalyst. When using halogenated titanium compounds or metal halides such as magnesium halides as solid catalysts, it is required that the polymerization activity per solid catalyst be sufficiently high in order to prevent corrosion of equipment and equipment caused by active halogens. There is. From this point of view, catalysts in which transition metal compounds such as titanium tetrachloride are supported on carriers such as magnesium compounds, which have been actively developed in recent years, are extremely unsatisfactory in terms of polymerization activity per solid catalyst. Many (Belgium Patent No. 759601, Special Publication No. 1973)
-46269, Special Publication No. 47-26383, etc.). In addition, as a catalyst system for obtaining a solid product by transferring a titanium compound with an organomagnesium, a solid catalyst component consisting of a Grignard reagent and titanium tetrachloride or alkoxy-containing titanium halide (Japanese Patent Application Laid-Open No. 46-1988-1) is used.
Publication No. 4391, Special Publication No. 47-40959, Special Publication No. 1972
-39470, Japanese Patent Publication No. 50-30102) and a solid catalyst component consisting of a Grignard reagent reacted with an alkoxy-containing halogenated titanium compound and further treated with titanium tetrachloride (Japanese Patent Publication No. 57-24361, Japanese Patent Publication No. 50-30102). However, it is insufficient in terms of polymerization activity per transition metal and polymerization activity per solid catalyst component. <Problems to be Solved> Under the present circumstances, the problem to be solved by the present invention, that is, the purpose of the present invention is to achieve sufficient catalytic activity per transition metal and per solid catalyst component so that removal of catalyst residue is unnecessary. Using high solid catalyst components,
An object of the present invention is to provide a method for producing an olefin polymer. <Means to Solve the Problems> The present invention provides: (A) In the coexistence of alcohols and/or phenolic compounds, the general formula Ti(OR ¹ ) _o X _4-o (R ¹ has 1 to 20 carbon atoms) , X is a halogen atom, and n is a number of 0<n≦4. Production of an olefin polymer, characterized in that olefin is homopolymerized or copolymerized using a catalyst system consisting of a trivalent titanium compound-containing solid catalyst component obtained by treatment with a mixture of (B) and an organoaluminum compound. It is about law. The use of the present catalyst system achieves the above objectives. The present invention will be explained in detail below. (a) Titanium compound The titanium compound used in the present invention has the general formula Ti(OR ¹ ) _o X _4-o (R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, and n is 0< n≦4
represents the number of ). Specific examples of R ¹ include methyl, ethyl, n-propyl,
iso-propyl, n-butyl, iso-butyl, n
-amyl, iso-amyl, n-hexyl, n-
Alkyl groups such as heptyl, n-octyl, n-decyl, n-dodecyl, phenyl, cresyl,
Examples include aryl groups such as xylyl and naphthyl, cycloalkyl groups such as cyclohexyl and cyclopentyl, alkenyl such as propenyl, and aralkyl groups such as benzyl. Alkyl group having 2 to 18 carbon atoms and 6 to 18 carbon atoms
18 aryl groups are preferred. Especially carbon number 2-18
A straight-chain alkyl group is preferred. It is also possible to use titanium compounds having two or more different OR ¹ groups. Examples of the halogen atom represented by X include chlorine, bromine, and iodine. In particular, chlorine gives favorable results. The value of n in the titanium compound represented by the general formula Ti(OR ¹ ) _o x _4-o is 0<n≦4, preferably 2≦n≦4, particularly preferably n=4. A known method can be used to synthesize the titanium compound represented by the general formula Ti(OR ¹ ) _o x _4-o (0<n≦4). For example, a method in which Ti(OR ¹ ) ₄ and TiX ₄ are reacted at a predetermined ratio, or a method in which TiX ₄ and a corresponding alcohol are reacted in a predetermined amount can be used. (b) Alcohols and phenols In the synthesis of component (A) of the present invention, alcohols with a carbon number of 2 to 15
Alcohols having 6 to 25 carbon atoms or phenols having 6 to 25 carbon atoms are used. Specific examples of alcohols include methanol,
Ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol,
tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, caprylic alcohol, nonyl alcohol,
aliphatic saturated alcohols such as decyl alcohol,
Aliphatic unsaturated alcohols such as allyl alcohol, crotyl alcohol, and propargyl alcohol; alicyclic alcohols such as cyclopentanol and cyclohexanol; benzyl alcohol;
Methylbenzyl alcohol, ethylbenzyl alcohol, n-propylbenzyl alcohol,
Aromatic alcohols such as isopropyl alcohol, dimethylbenzyl alcohol, diethylbenzyl alcohol, di-n-propylbenzyl alcohol, and diisopropylbenzyl alcohol are mentioned. Specific examples of phenols include phenol, θ-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-
xylenol, 3,4-xylenol, 3,5
-xylenol, carvacrol, thymol,
Examples include α-naphthol and β-naphthol. Among these, aliphatic alcohols having 1 to 4 carbon atoms and phenols having 6 to 10 carbon atoms are preferred. (c) Organomagnesium compound Next, the organomagnesium used in the present invention is:
Any type of organomagnesium compound having a magnesium-carbon bond can be used. In particular, ^the general formula R ⁹ M _g
~20 hydrocarbon groups, and X represents a halogen. )
Grignard compound and general formula represented by
R ¹⁰ R ¹¹ Mg (in the formula, R ¹⁰ and R ¹¹ have 1 to 1 carbon atoms)
Represents 20 hydrocarbon groups. ) are preferably used. here
R ⁹ , R ¹⁰ and R ¹¹ may be the same or different,
Methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl,
n-amyl, iso-amyl, n-hexyl, n
-octyl, 2-ethylhexyl, phenyl,
Indicates an alkyl group having 1 to 20 carbon atoms such as benzyl, an aryl group, an aralkyl group, and an alkenyl group. Specifically, as Grignard compounds, methylmagnesium chloride, ethylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium iodide, n-propylmagnesium chloride, n-propylmagnesium bromide, n-butylmagnesium chloride, n-butylmagnesium bromide, sec−
Butylmagnesium chloride, sec-butylmagnesium bromide, tert-butylmagnesium chloride, tert-butylmagnesium bromide, n-amylmagnesium chloride, iso-
Amylmagnesium chloride, phenylmagnesium chloride, phenylmagnesium bromide, etc. are compounds represented by R ¹⁰ R ¹¹ Mg such as diethylmagnesium, di-n-propylmagnesium, di-iso-propylmagnesium,
Di-n-butylmagnesium, di-sec-butylmagnesium, di-tert-butylmagnesium, n-butyl-sec-butylmagnesium,
Examples include di-n-amylmagnesium and diphenylmagnesium. As the synthesis solvent for the above organomagnesium compound, diethyl ether, di-n-propyl ether, di-iso-propyl ether, di-
n-butyl ether, di-iso-butyl ether, di-n-amyl ether, di-iso-amyl ether, di-n-hexyl ether, di-
n-octyl ether, diphenyl ether,
Ether solvents such as dibenzyl ether, phenethole, anisole, tetrahydrofuran, and tetrahydropyran can be used. Further, a hydrocarbon solvent such as hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, or a mixed solvent of an ether solvent and a hydrocarbon solvent may be used. The organomagnesium compound is preferably used in the form of an ether solution. As the ether compound in this case, an ether compound containing 6 or more carbon atoms in the molecule or an ether compound having a cyclic structure is used. In particular, it is preferable to use the Grignard compound represented by R ⁹ MgCl in the form of an ether solution from the viewpoint of catalytic performance. Hydrocarbon-soluble complexes of the above organomagnesium compounds and organometallic compounds can also be used. Examples of organometallic compounds include Li,
Examples include organic compounds of Be, B, Al or Zn. (d) Ether compounds The ether compounds used in the present invention include diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, di-n-amyl ether, diisoamyl ether, and dineobenchi. Preferred are dialkyl ethers such as ether, di-n-hexyl ether, di-n-octyl ether, methyl-n-butyl ether, methyl-isoamyl ether, and ethyl-isobutyl ether. Particularly preferred are di-n-butyl ether and diisoamyl ether. (e) Synthesis of solid catalyst component (A) The solid catalyst component (A) of the present invention is a titanium compound represented by the general formula Ti(OR ¹ ) _o X _4-o in the coexistence of an alcohol and/or a phenol compound. It is synthesized by reducing the compound with an organomagnesium compound and treating the solid product with a mixture of an ether compound and titanium tetrachloride. All synthetic reactions are carried out under an inert gas atmosphere such as nitrogen or argon. First, as a method for the reduction reaction of a titanium compound with an organomagnesium compound, there is a method of adding an organomagnesium compound to a mixture of a titanium compound and an alcohol or a phenol compound, or conversely, a method of adding a titanium compound to a solution of an organomagnesium compound. and a mixture of alcohols or phenolic compounds may be added. The titanium compound and the alcohol or phenol compound are preferably used after being dissolved or diluted in a suitable solvent. Such solvents include hexane, heptane,
Aliphatic hydrocarbons such as octane and decane; aromatic hydrocarbons such as toluene, xylene and decalin;
Examples include alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, and ether compounds such as diethyl ether, dibutyl ether, diisoamyl ether, and tetrahydrofuran. The reduction temperature is -50 to 70°C, preferably -30 to
The temperature range is 50°C, particularly preferably -25 to 35°C. There is no particular restriction on the dripping time, but it is usually 30 minutes to 6 minutes.
It takes about an hour. After the completion of the reduction reaction, an additional 20~
The post-reaction may be carried out at a temperature of 120°C. The amount of alcohol or phenol compound to be used is the molar ratio of hydroxyl group to titanium atom in the titanium compound: hydroxyl group/Ti=0.5 to 50, preferably 1 to 30, particularly preferably 3 to 25. In addition, the amount of organic magnesium compound used is
The molar ratio of the sum of titanium atoms and hydroxyl groups to magnesium atoms is Ti+hydroxyl/Mg=0.1 to 10, preferably 0.2 to 5.0, particularly preferably 0.5 to 2.0. Furthermore, when synthesizing a solid product by a reduction reaction, it is also possible to coexist a porous substance such as silica gel, alumina, or a porous polymer, and to impregnate the solid product into the porous substance. Such porous materials are spherical and have a particle size of 10 to
Silica gel and alumina having a pore volume of 200 μm and a pore volume of 0.5 ml/g or more are preferred. The solid product obtained by the reduction reaction is separated into solid and liquid, and washed several times with an inert hydrocarbon solvent such as hexane or heptane. The solid product obtained by the above method is then treated with a mixture of an ether compound and titanium tetrachloride. The treatment of the solid product with the mixture of ether compound and titanium tetrachloride is preferably carried out in the form of a slurry. Solvents used for slurrying include pentane, hexane, heptane,
Aliphatic hydrocarbons such as octane and decane; aromatic hydrocarbons such as toluene, xylene and decalin;
Examples include alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, and halogenated hydrocarbons such as dichloroethane, trichloroethane, trichloroethylene, monochlorobenzene, dichlorobenzene, and trichlorobenzene. Slurry concentration is 0.05-0.5g solids/ml solvent,
Particularly preferred is 0.1 to 0.3 g solid/ml solvent. Reaction temperature is 30~150℃, preferably 45~120℃
℃, particularly preferably 60 to 100℃. There is no particular restriction on the reaction time, but 30 minutes to 6 hours is usually suitable. The methods for adding the solid product, ether compound and titanium tetrachloride include adding the ether compound and titanium tetrachloride to the solid product, and conversely adding the solid product to a solution of the ether compound and titanium tetrachloride. Either method may be used. In the method of adding an ether compound and titanium tetrachloride to a solid product, a method of adding the ether compound and then adding titanium tetrachloride, or a method of adding the ether compound and titanium tetrachloride simultaneously, especially a method of adding the ether compound and titanium tetrachloride in advance. A method of adding a mixture of titanium is preferred. The reaction of the solid product with the ether compound and titanium tetrachloride may be repeated two or more times. The amount of the ether compound to be used is 0.1 to 100 per mole of titanium atoms contained in the solid product.
mol, preferably from 0.5 to 50 mol, particularly preferably from 1 to 20 mol. The amount of titanium tetrachloride added is 1 to 1000 mol, preferably 3 to 500 mol, particularly preferably 3 to 500 mol, per 1 mol of titanium atoms contained in the solid product.
10 to 300 moles. In addition, ether compound 1
The amount of titanium tetrachloride added per mole is 1 to
100 mol, preferably 1.5 to 75 mol, particularly preferably 2 to 50 mol. The trivalent titanium compound-containing solid catalyst component obtained by the above method is separated into solid and liquid, washed several times with an inert hydrocarbon solvent such as hexane or heptane, and then used for polymerization. After solid-liquid separation, it is washed once or more with an excess amount of an aromatic hydrocarbon such as toluene or xylene or a halogenated hydrocarbon such as monochlorobenzene at a temperature of 50 to 120°C, and then washed with an excess amount of an aromatic hydrocarbon such as toluene or xylene or a halogenated hydrocarbon such as monochlorobenzene, and then washed with an excess amount of an aromatic hydrocarbon such as toluene or xylene or a halogenated hydrocarbon such as monochlorobenzene. It may be used for polymerization after repeated washing with a solvent several times. In addition, for the purpose of improving the stereoregularity of the polymer,
It is also possible to add known ester compounds before or during the treatment of the solid product with the mixture with the ether compound and titanium tetrachloride. Such ester compounds are mono- and polyvalent carboxylic esters, such as aliphatic carboxylic esters, olefin carboxylic esters, alicyclic carboxylic esters, and aromatic carboxylic esters. Specific examples include methyl methacrylate, ethyl benzoate, butyl benzoate, methyl toluate, ethyl toluate, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, maleic acid. dibutyl acid, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n phthalate
-butyl, diisobutyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, diphenyl phthalate, and the like. Among these ester compounds, olefin carboxylic acid esters such as methacrylic acid esters and maleic acid esters, aromatic carboxylic acid esters such as benzoic acid esters, and phthalic acid esters are preferred. The amount of ester compound used is from 0.1 to 50 mol, preferably from 0.3 to 20 mol, particularly preferably from 0.5 to 10 mol, per mole of titanium atom in the solid product. In addition, the amount of ester compound used per mol of magnesium atom in the solid product is 0.01 to 1.0.
mol, preferably 0.03 to 0.5 mol. (f) Organoaluminum compound (B) In the present invention, an organoaluminum compound (B) used in combination with the above-mentioned solid catalyst component (A).
has at least one Al-carbon bond in the molecule. A typical formula is shown below. R ¹² 〓AlY _3- 〓 R ¹³ R ¹⁴ Al-O-AlR ¹⁵ R ¹⁶ Here, R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are hydrocarbon groups having 1 to 8 carbon atoms, Y is halogen,
Represents hydrogen or an alkoxy group. γ is 2≦γ
It is a number expressed as ≦3. Specific examples of organoaluminum compounds include:
Trialkyl aluminum such as triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, dialkyl aluminum hydride such as diethyl aluminum hydride and diisobutyl aluminum hydride, dialkyl aluminum halide such as diethyl aluminum chloride, mixture of trialkyl aluminum and dialkyl aluminum halide, tetraethyl aluminum hydride, etc. Examples include alkylalumoxanes such as alumoxane and tetrabutyldialumoxane. Among these organoaluminum compounds, trialkylaluminum, a mixture of trialkylaluminium and dialkylaluminium halide, and alkylalumoxane are preferred, and triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride, and tetraethyldialumoxane are particularly preferred. preferable. The amount of the organoaluminum compound to be used can be selected within a wide range, such as from 1 to 1000 mol per mol of titanium atom in the solid catalyst, but in particular from 5 to 1,000 mol per mol of titanium atom in the solid catalyst.
A range of 600 moles is preferred. (g) Olefin polymerization method There are no particular restrictions on the method of supplying each catalyst component to the polymerization tank, except that it is supplied in an inert gas such as nitrogen or argon without moisture. Catalyst components (A) and (B) may be supplied separately,
They may be supplied in contact with each other in advance. Polymerization can be carried out at temperatures ranging from -30 to 200°C. Although there are no particular limitations on the polymerization pressure, a pressure of about 3 to 100 atm is desirable from the viewpoint of industrial and economical considerations. The polymerization method can be either continuous or batchwise. Also,
Slurry polymerization using an inert hydrocarbon solvent such as propane, butane, pentane, hexane, heptane, or octane, liquid phase polymerization without a solvent, or gas phase polymerization is also possible. Next, olefins that can be applied to the present invention have a carbon number of 2 or more, and specific examples include ethylene, propylene, butene-1, pentene-1, and pentene-1.
1, hexene-1,3-methyl-pentene-
Examples include 1,4-methyl-pentene-1, but the present invention is not limited to the above compounds. The polymerization according to the present invention can be either homopolymerization or copolymerization. During copolymerization, a copolymer can be obtained by contacting two or more types of olefins in a mixed state. Further, heteroblock copolymerization in which polymerization is carried out in two or more stages can also be easily carried out. It is also possible to add chain transfer agents such as hydrogen to adjust the molecular weight of the polymer. It is also possible to add a known electron-donating compound to the polymerization system as a third component for the purpose of improving the stereoregularity and molecular weight of the polymer. Examples of such electron-donating compounds include the following compounds. These include organic carboxylic acid esters such as methyl methacrylate and methyl toluate, phosphite esters such as triphenylphosphite, and silicate esters such as tetraethoxysilane and phenyltriethoxysilane. Silicate ester compounds and benzoate ester compounds are preferred. Silicate ester compounds are particularly preferred. Specific examples of silicate ester compounds include tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane,
Phenylmethyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, butyltriethoxysilane, tetrabutoxysilane , vinyltributoxysilane, diethyldiethoxysilane and the like. The amount of these electron-donating compounds to be used is per mole of organoaluminum compound as component (B).
The amount is 0.01 to 5 mol, preferably 0.03 to 3 mol, particularly preferably 0.05 to 1 mol. <Examples> The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Example 1 (A) Synthesis of organomagnesium compound After purging the flask in No. 1 equipped with a stirrer, reflux condenser, dropping funnel and thermometer with argon, grinded magnesium 32.0 g
g was added. A dropping funnel was charged with 120 g of n-butyl chloride and 500 ml of di-n-butyl ether, and about 30 ml of the mixture was added dropwise to the magnesium in the flask to initiate the reaction. After starting the reaction, at 50℃
Continue dropping over a period of time, and after finishing dropping, raise the temperature to 60°C.
The reaction was continued for another hour. Thereafter, the reaction solution was cooled to room temperature and the solid content was separated. When n-butylmagnesium chloride in this di-n-butyl ether was hydrolyzed with 1N sulfuric acid and the concentration was determined by back titration with a 1N aqueous sodium hydroxide solution (phenolphthalein was used as an indicator), the concentration was 2.2 It was mol/. (B) Synthesis of solid product After purging a 300 ml flask equipped with a stirrer and a dropping funnel with argon, add 100 ml of n-heptane and 2.5 g (7.4 g) of tetrabutoxytitanium.
13.0 g (140 mmol) of phenol were added. Next, 66.7 ml of the organomagnesium compound synthesized in (A) was gradually added dropwise from the dropping funnel over 2 hours while maintaining the temperature inside the flask at 5°C. After the dropwise addition was completed, the mixture was further stirred at room temperature for 1 hour, and solid-liquid separation was performed at room temperature.
After repeated washing three times with 100 ml of heptane, the product was dried under reduced pressure to obtain 32.0 g of an off-white solid product. (C) Synthesis of solid catalyst component Solid product synthesized by reduction reaction of (B) after purging a flask with an internal volume of 100 ml with argon.
4.7 g, 25 ml of monochlorobenzene and 1.2 ml (4.5 mmol) of diisobutyl phthalate,
The reaction was carried out at 80°C for 1 hour. After the reaction, solid-liquid separation was performed, and 30ml of n-heptane was added.
Washed twice. After washing, add 25% monochlorobenzene to the flask.
ml, n-butyl ether 1.6 ml (9.5 mmol)
and 28 ml (250 mmol) of titanium tetrachloride were added, and the reaction was carried out at 80°C for 3 hours. After the reaction is complete,
After solid-liquid separation at 80°C, washing was performed twice with 30 ml of monochlorobenzene at the same temperature. The treatment with the mixture of n-butyl ether and titanium tetrachloride described above was repeated once again under the same conditions, and the mixture was washed twice with 30 ml of n-heptane and then dried under reduced pressure to obtain 2.4 g of an orange-white solid catalyst component. The solid catalyst component contains 1.3% by weight of titanium atoms,
It contained 12.9% by weight of phthalate ester. (D) Polymerization of propylene After purging a stainless steel autoclave with internal volume of 130 ml and stirring with a magnetic stirrer with argon, triethylaluminum
0.57 mmol, phenyltriethoxysilane
0.057 mmol and 7.2 of the solid catalyst component obtained in (C) above
mg, and 80 ml of liquefied propylene were charged into an autoclave. The autoclave was kept at 60°C for 1 hour with stirring. After releasing the excess propylene, the resulting polypropylene was air-dried overnight. 15.1
g of polypropylene was obtained. Therefore, the yield (g) of polypropylene per gram of solid catalyst component (hereinafter abbreviated as PP/cat) is
When PP/cat=2090, the yield (g) of polypropylene per titanium (hereinafter abbreviated as PP/Ti) is PP/Ti
= 161000. In addition, the obtained polypropylene powder was boiled
- The percentage of the residue extracted with heptane for 6 hours (hereinafter abbreviated as IY (%)) was IY = 98.3%. Comparative Example 1 (A) Synthesis of Solid Product A 300 ml flask equipped with a stirrer and a dropping funnel was purged with argon, and then 60 ml of n-heptane and 27.3 g (80 mmol) of tetrabutoxytitanium were charged. Next, 36.4 ml of the organomagnesium compound synthesized in Example 1 (A) was gradually added dropwise from the dropping funnel over 3 hours while maintaining the temperature inside the flask at 5°C. After the dropwise addition was completed, the mixture was stirred for another 2 hours at room temperature, then solid-liquid was separated at room temperature, washed three times with 60 ml of n-heptane, and dried under reduced pressure to obtain a deep green solid product.
28.9g was obtained. (B) Synthesis of solid catalyst component In the synthesis of the solid catalyst component in (C) of Example 1, chlorobenzene was replaced during the treatment with diisobutyl phthalate and the first treatment with a mixture of n-butyl ether and titanium tetrachloride. A solid catalyst component was synthesized in the same manner as in Example 1 (C) except that n-heptane was used. The solid catalyst component contains 14.2% by weight of titanium atoms,
It contained 1.9% by weight of phthalate esters. (C) Polymerization of propylene Propylene was polymerized in the same manner as the polymerization of propylene in (D) of Example 1. The result is
PP/cat=2440, PP/Ti=17200, IY=80.4%
It was hot. Compared to Example 1, when phenol is not present, the activity and stereoregularity per titanium are significantly lower. Examples 2 to 5 Example 1 except that the alcohols or phenols shown in Table 1 were used instead of phenol in the synthesis of the solid product in (B) of Example 1.
A solid catalyst component was synthesized in the same manner as in Example 1 (D), and propylene was polymerized in the same manner as in Example 1 (D). The results are shown in Table-1.

[Table] Example 6 (A) Organomagnesium in silica gel Silica gel (average particle size 100 μm, pore volume 1.0
ml/g, average pore radius 100Å) was added,
Drying was performed under reduced pressure at 100°C for 30 minutes. After drying, the inside of the flask was purged with argon, 120 ml of n-butyl ether was added, and a stirrer was attached.
Next, 84 ml of the organomagnesium compound synthesized in Example 1 (A) was added dropwise from the dropping funnel over 1 hour while maintaining the temperature inside the flask at 80°C, and the mixture was further treated at the same temperature for 30 minutes. Then, once with 120 ml of n-butyl ether, twice with 120 ml of n-heptane.
After repeated washing, 32.3 g of organic magnesium-treated silica gel was obtained by drying under reduced pressure. (B) Synthesis of a solid product supported on silica gel After purging a 100 ml flask equipped with a stirrer and a dropping funnel with argon, the organomagnesium-treated product of silica gel synthesized in (A) 4.8
g and n-butyl ether 24 ml, tetrabutoxytitanium 0.28 g (0.82 mmol), phenol 1.3
g (14 mmol) and stirred at room temperature for 45 minutes. Next, 7.4 ml of the organomagnesium compound synthesized in Example 1 (A) was added dropwise from the dropping funnel over 1 hour while maintaining the temperature inside the flask at 5°C. After dropping, incubate at 55℃ for 30 minutes and then at room temperature for 1 hour.
After stirring for an hour, washing with 30 ml of n-heptane three times and drying under reduced pressure yielded a grayish-white solid product.
5.7g was obtained. (C) Synthesis of solid catalyst component A solid product synthesized by the reduction reaction of (B) after purging a flask with an internal volume of 100 ml with argon.
5.5 g, 28 ml of monochlorobenzene and 0.23 ml (0.86 mmol) of diisobutyl phthalate were added.
The reaction was carried out at 80°C for 1 hour. After the reaction, the solid and liquid were separated and washed three times with 30 ml of n-heptane. After washing, add 28 ml of monochlorobenzene and 0.3 ml of n-butyl ether to the flask.
(1.8 mmol) and titanium tetrachloride 5.3 ml (47
mmol) was added thereto, and the reaction was carried out at 80°C for 3 hours. After the reaction, solid-liquid separation was carried out at 80°C, followed by washing twice with 30 ml of monochlorobenzene at the same temperature. The above-mentioned treatment with the mixture of n-butyl ether and titanium tetrachloride was repeated once again under the same conditions, and the mixture was washed twice with 30 ml of n-heptane and then dried under reduced pressure to obtain 2.4 g of an orange-white solid catalyst component. This solid catalyst component contains 4.2 titanium atoms.
It contained 1.0% by weight of phthalate ester. When propylene was polymerized using the above solid catalyst component in the same manner as in Example 1 (D), PP/cat=880, PP/Ti=21000, IY=
It was 96.6%. The polymer had a spherical shape and a bulk density of 0.42 g/cm ² . Example 7 In the synthesis of the solid product of Example 6 (B), n-
Propylene was polymerized in the same manner as in Example 6, except that n-heptane was used instead of butyl ether and ethanol was used instead of phenol. The results are PP/cat=640, PP/Ti=
16800, IY=94.5%, and bulk density 0.43 g/cm ³ . Example 8 (A) Synthesis of solid catalyst component A solid catalyst component was synthesized in the same manner as in Example 3, except that the treatment with diisobutyl phthalate was not performed in the synthesis of the solid catalyst component in Example 8. This solid catalyst component contained 4.4% by weight of titanium atoms. (B) Polymerization of ethylene Next, a 0.4 liter autoclave equipped with a stirrer was sufficiently purged with argon, and then 90 g of butane was charged therein. After raising the temperature to 60°C, 6 kg/cm ² of ethylene was added to bring the total pressure to 15 kg/cm ² . The above solid catalyst components
Polymerization was started by adding 4.9 mg and 1 mmol of triethylaluminum. After that, ethylene was continuously supplied to keep the total pressure constant and the temperature was increased to 1.
Time polymerization was carried out. After the polymerization was completed, the resulting polymer was filtered and dried under reduced pressure at 60°C. The polymerization characteristics at this time were 107,000 g.polymer/g.titanium. Comparative Example 2 (A) Synthesis of Solid Product A solid product was synthesized in the same manner as in Comparative Example 1 (A). (B) Synthesis of solid catalyst component The solid catalyst component was synthesized in the same manner as in (C) of Example 1, except that the treatment with diisobutyl phthalate was not performed in the synthesis of the solid catalyst component in (C) of Example 1. Synthesized. This solid catalyst component contained 18.6% by weight of titanium atoms. (C) Polymerization of ethylene Ethylene was polymerized in the same manner as the polymerization of ethylene in Example 8 (B). Its polymerization activity is
It was 38,300 g of polymer/g of titanium. Compared to Example 8, when ethanol is not present, the activity per titanium is significantly lower. <Effects of the Invention> As described above, by using the catalyst system of the present invention, the catalytic activity per solid catalyst and per titanium atom is extremely high. It is possible to produce an olefin polymer with an extremely low content of halogen atoms and titanium atoms, which are closely related to the coloration, stability, and corrosion properties of the polymer. That is, equipment for removing catalyst residues is not required, and the production cost of the olefin polymer can be reduced.

[Brief explanation of the drawing]

FIG. 1 is a flowchart to aid in understanding the present invention. This flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited thereto.

Claims (1)

[Claims] 1 (A) In the coexistence of alcohols and/or phenolic compounds, general formula Ti (OR ¹ ) _o X _4-o (R ¹
represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, and n represents a number satisfying 0<n≦4. ) A solid catalyst component containing a trivalent titanium compound obtained by treating a solid product obtained by reducing a titanium compound represented by (B) with an organomagnesium compound with a mixture of an ether compound and titanium tetrachloride; A method for producing an olefin polymer, which comprises homopolymerizing or copolymerizing an olefin using a catalyst system comprising an aluminum compound.